EP2528963B1 - Polymers made of renewable resources - Google Patents

Description

The invention relates to polycondensates having longer linear methylene sequences in the main chain, processes for their preparation, their use and a catalytic process for the preparation of the monomers.

Renewable resources are of interest as an alternative to finite fossil resources. In addition, novel materials with advantageous properties can be accessible. For this, it is desirable that the molecular structure of the raw material also be reflected in the structure of the resulting products.

An attractive characteristic of vegetable oils and fats is the linear hydrocarbon structure of the fatty acids (in the form of triglycerides). This has long been used for the production of the engineering plastic polyamide-11 starting from ricinoleic acid. In this case, however, only part of the fatty acid molecule is used. The thermal rearrangement of ricinoleic acid leads to cleavage of the fatty acid chain to undec-10-enoic acid, which is further converted to the polyamide-11, and heptanal as a byproduct. In addition, the underlying rearrangement reaction requires the presence of the hydroxy group adjacent to the double bond and is therefore limited to ricinoleic acid and its derivatives among the currently technically available fatty acids. From ricinoleic acid also sebacic acid is accessible, which is converted to polycondensates such as polyamide-6,10. In this case, the by-product is 2-octanol.

A complete linear incorporation of long chain C _{> 20} fatty acids into polymers is desirable because it would make full use of the substrate to build up the polymers and allow long linear methylene sequences to produce desirable properties such as crystallinity and associated melting and crystallization points , mechanical and other Application properties, mixing behavior in polymer blends, or low water absorption. By dimerization fatty acids can be converted to the so-called dimer fatty acids, but which have a branched, non-linear structure and lead to non-crystalline segments ( Angew. Chem. 2000, 112, 2292 ). Complete linear incorporation of fatty acids into monomers and polymers produced therefrom is difficult to realize because the reactive double bond of unsaturated fatty acids is in the middle of the molecule and the terminal methyl group is less reactive. In the implementation of raw materials from renewable sources is generally to be considered that these usually contain impurities, which can interfere with the conversion process and lead to product mixtures instead of pure substances. For example, different fatty acids or their derivatives often have a different spectrum of contaminants depending on their biological origin.

In addition, most synthetic methods for longer-chain α, ω-dicarboxylic acids or their derivatives, regardless of their practicality and the nature and availability of the starting materials, lead to the even-numbered products.

The catalytic alkoxycarbonylation of olefins, that is, the reaction with carbon monoxide and an alcohol, is a known reaction for producing esters (US Pat. Applied Homogeneous Catalysis with Oiganornaetallic Compounds, eds. B. Cornils and WA Herrmann, Wiley-VCH, Weinheim, 2000 ). Thus, the cobalt-catalyzed conversion of methyl esters of monounsaturated fatty acids unselective leads to 60:40 mixtures of linear α, ω-dicarboxylic acid dimethyl ester and branched diesters ( Fats, soaps, paints 1985, 87, 403 ). For the methoxycarbonylation of ethylene, it has been found that a palladium (II) catalyst modified by 1,2- bis [(di-tert-butylphosphino) methyl] benzene is particularly well suited ( Chem. Commun. 1999, 1877 ). Remarkably, these catalysts also convert internal olefins, such as 4-octene, into the linear methyl esters ( Chem. Commun. 2004, 1720 ). The analogous reaction in methanolic solution of the internally unsaturated C ₁₈ fatty acid methyl ester Methyloleate, as well as the polyunsaturated analogues methyl linoleate and methyl linolenate, preferably leads to the saturated α, ω-dicarboxylic acid ester, 1,19-dimethylnonadecanedioate ( Inorg. Chen. Commun. 2005, 8, 878 ). However, this was not obtained in the purity required for the production of polycondensates ( Trans. Faraday Soc. 1936, 32, 39 ).

Erucic acid is an example of an unsaturated, well-available C _{> 20} fatty acid. The reaction of methyl erucate with carbon monoxide in methanol with trialkyl diphosphine-modified palladium (II) catalyst proved to be problematic, no satisfactory alkoxycarbonylation was observed. Surprisingly, however, it has been found that with erucic acid and other unsaturated fatty acids containing more than 20 carbon atoms (C _{> 20} fatty acids) in higher alcohols, the reaction is selective to α, ω-dicarboxylic acid esters and these are obtained in purities of> 99%.

Furthermore, it has been found that the corresponding α, ω-dicarboxylic acids and their esters, and their reduced hydroxy and amino derivatives are outstandingly suitable as monomers for the preparation of polycondensates.

Z, Z'

ist gleich oder verschieden -X-C(=O)∼, -C(=O)-HN-CH₂∼, -C(=O)-O-CH₂∼, -NH-C(=O)-O-CH₂∼ -O-C(=O)-NH-CH₂∼;

X

ist O oder NH;

∼

gibt die Bindung an die Gruppe (CH₂)_2n+1 an und

n

ist eine Zahl ≥ 10.

The invention therefore relates to a polycondensate containing one or more repeating units of the formula (I),

-Z- (CH ₂ ) _{2n + 1} -Z ^' - (I),

wherein the symbols and indices have the following meanings:

Z, Z '

is the same or different -XC (= O) -, -C (= O) -HN-CH ₂ -, -C (= O) -O-CH ₂ -, -NH-C (= O) -O-CH ₂ ~ -OC (= O) -NH-CH ₂ ~;

X

is O or NH;

~

indicates the bond to the group (CH _{2) 2n + 1,} and

n

is a number ≥ 10.

Z¹, Z^1'

∼C(=O)-Q oder ∼CH₂-NCO ist;

Q

gleich oder verschieden OH, Halogen oder C₁-C₁₀-Alkoxy ist;

∼

die Bindung an die Gruppe (CH₂)_2n+1 angibt und

n

eine Zahl ≥ 10 ist,

mit mindestens einem Di- oder Polyol oder mindestens einem Di- oder Polyamin polykondensiert wird,
und/oder
mindestens eine monomere Verbindung der Formel (III),

        Z²-(CH₂)_2n+1-Z^2'     (III),

worin

Z², Z²'

gleich oder verschieden HO-CH₂∼ oder H₂N-CH₂∼ ist

∼

die Bindung an die Gruppe (CH₂)_2n+1-Gruppe angibt und

n

eine Zahl ≥ 10 ist,

mit mindestens einer Di- oder Polycarbonsäure, einem reaktiven Derivat einer solchen Di- oder Polycarbonsäure oder mindestens einem Di- oder Polyisocyanat polykondensiert.The invention further provides a process for the preparation of the polycondensate according to the invention, where at least one monomeric compound of the formula (II)

Z ¹ - (CH ₂ ) _{2n + 1} -Z ^{1 '} (II)

wherein

Z ¹ , Z ^{1 '}

~C (= O) -Q or ~CH ₂ -NCO;

Q

is the same or different OH, halogen or C ₁ -C ₁₀ alkoxy;

~

indicates the binding to the group (CH ₂ ) _{2n + 1} and

n

a number ≥ 10,

is polycondensed with at least one di- or polyol or at least one di- or polyamine,
and or
at least one monomeric compound of the formula (III),

Z ² - (CH ₂ ) _{2n + 1} -Z ^{2 '} (III),

wherein

Z ² , Z ² '

is the same or different HO-CH ₂ ~ or H ₂ N-CH ₂ ~

~

indicates the bond to the group (CH ₂ ) _{2n + 1} group and

n

a number ≥ 10,

polycondensed with at least one di- or polycarboxylic acid, a reactive derivative of such a di- or polycarboxylic acid or at least one di- or polyisocyanate.

The invention furthermore relates to the use of the polycondensate according to the invention in moldings, coatings, foams, films, films and / or fibers, as well as the corresponding articles which comprise the polycondensate according to the invention.

The invention likewise relates to a process for the preparation of saturated or unsaturated α, ω-dicarboxylic acids or esters with 2n + 3 in each case Carbon atoms in the acid moiety, where n≥10, comprising the step of hydroxy- or alkoxycarbonylation of a monounsaturated or polyunsaturated fatty acid ester having 2n + 2 carbon atoms in the acid moiety, where n≥10, in the presence of a catalyst containing at least one palladium compound and at least one Phosphine at a temperature in the range of 50 to 120 ° C and a pressure of 3 to 80 atm.

The monomers for preparing the polycondensates according to the invention are obtained according to the invention by hydro- or alkoxycarbonylation of unsaturated fatty acids having at least 22 C atoms. The reaction takes place in the presence of a catalyst.

The catalyst used is characterized in that it contains a palladium compound and at least one phosphorus-containing ligand which can coordinate via one or more phosphorus atoms at the metal center. In the phosphorus-containing ligands are as substituents R " ¹ -R" ³ on the phosphorus atom PR " ¹ R" ² R " ³ , independently of one another the same or different H, open-chain or cyclic aliphatic radicals C ₁ to C ₃₀ , aromatic radicals C ₁ to C. ₃₀ , in particular C ₅ -C ₁₂ , and via heteroatoms such as N, O or S bonded open-chain or cyclic aliphatic radicals C ₁ to C ₃₀ and aromatic radicals C ₁ to C ₃₀ , in particular C ₅ -C ₁₂ , are suitable " ¹ to R" ³ may also contain in the side chain heteroatoms, such as O, N, S or P. Particularly suitable radicals are tert-butyl groups.The ligand may contain a plurality of phosphorus atoms bridged via one or more of the radicals R " are. Particularly suitable bridging radicals are those which bridge the phosphorus atoms over three or four atoms. Particularly suitable bridging radicals are -CH ₂ -C ₆ H ₄ -CH ₂ - and - (CH ₂ ) ₃ -.

Phosphanes are preferably used. Trialkyl phosphines and bidentate phosphines are particularly preferably used. Examples of suitable phosphorus ligands are: 1,3-bis (di-tert-butylphosphino) propane; 1,3-bis butane (di-tert-butylphosphino); 1,3-bis (di-tert-butylphosphino) -2,2'-dimethyl-propane; 1,2-bis [(di-tert-butylphosphino) methyl] benzene; Benzene 1,2-bis [(cyclooct-1,5-diylphosphino) methyl]; 1,3-bis (cyclooct-1,5-diylphosphino) propane; 1 - [(di-tert-butylphosphino) methyl] -2- (di-tert-butylphosphino) benzene.

One type of phosphorus-containing ligand or a mixture of several phosphorus-containing ligands can be used.

Examples of suitable palladium compounds are palladium acetate, palladium hexanoate, palladium octanoate, bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, (1,5-cyclooctadiene) dimethylpalladium, (1,5-cyclooctadiene) dichloropalladium, (1,5-cyclooctadiene) methylchloropalladium, Tetrakis (acetonitrile) palladium (II) tetrafluoroborate and diacetonitrile dichloropalladium.

The catalyst optionally contains further components, for example organic and / or inorganic acids and / or salts thereof. Suitable further components which may be mentioned by way of example are trifluoromethanesulfonic acid, methanesulfonic acid, perchloric acid, p-toluenesulfonic acid, [H (OEt ₂ )] [BAr ^F ₄ ], NaBAr ^F ₄ with Ar ^F = 3,5-bis (trifluoromethyl) phenyl.

The catalyst components can be mixed together in any order. The mixture can be carried out in or outside the reaction vessel of the carbonylation. In particular, preformed palladium complexes of the phosphine can be used. Examples are [(diphosphine) PdX ₂ ] with X = methanesulfonate, trifluoromethanesulfonate, or tosylate.

Particularly suitable as a catalyst is a combination of a palladium (II) salt and 1,2-bis [(di-tert-butylphosphino) methyl] benzene, especially in combination with methanesulfonic acid.

The molecular ratio of palladium (II) compound to phosphorus in the phosphine ligand is generally from 1: 0.5 to 1: 100, preferably from 1: 0.5 to 1:20, more preferably from 1: 2 to 1:10 ,

The molecular ratio of Pd (II) compound to the optionally present acid is optionally from 1: 0.5 to 1: 200.

Suitable reaction media are the alcohols required for the alkoxycarbonylation. Preference is given to C ₂ -C ₃₆ alcohols, such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, n-octanol, isooctanol, 2-ethylhexanol, Cyclohexanol, 2-phenylethanol, phenol, and benzyl alcohol or mixtures. Also suitable are aprotic organic solvents such as methylene chloride, chloroform, dichloroethane, benzene, toluene, chlorobenzene, isobutane, hexane, heptane, octane, diethyl ether, diphenyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, N-methylpyrollidone, dimethylacetamide, acetone, cyclohexanone, triethylamine , Tributylamine and mixtures of these compounds. The reaction medium may generally contain up to 50% by volume of methanol, preferably less than 20% by volume of methanol. The reaction mixture may be anhydrous or contain water. For the preparation of α, ω-dicarboxylic acids used by the invention by Hydrocarbonylierung the presence of water is necessary. If an alkoxycarbonylation is carried out for the preparation of α, ω-diesters, the reaction mixture is preferably anhydrous.

Furthermore, the fatty acid ester used can also serve as the reaction medium. The reaction mixture can be monophase or polyphase. The reaction mixture preferably consists of only one liquid phase. During the reaction optionally reaction medium, reagents and catalyst or catalyst components can be added continuously or pulsed.

The temperature of the reaction mixture is in the range of -10 ° C to +200 ° C, preferably in the range of +50 ° C to 120 ° C, more preferably in the range of 85 ° C to 100 ° C. The pressure during the reaction is in the range of 0.1 to 200 atm, preferably 3 to 80 atm, more preferably 10 to 40 atm.

As a substrate, esters of mono- or polyunsaturated fatty acids having an even number of carbon atoms in the acid moiety, which are greater than 20 and preferably not greater than 34 is used. The symbol n in the formulas therefore stands for a natural number. Preference is given to mono- or polysubstituted, particularly preferably monounsaturated fatty acid esters having 22, 24, 26, 28, 30, 32 or 34 C atoms (in the acid moiety), particularly preferably 22, 24 or 26 C atoms, in particular 22 C atoms , Optionally, the free acids can also be used. Preferred esters of these fatty acids are esters of monofunctional alcohols, particularly preferably C ₁ -C ₁₀ -alkyl esters.

Particularly suitable are esters of erucic acid (cis-13-docosenoic acid), in particular the ethyl ester.

As substrates can be used esters of pure C _{> 20} fatty acids or technical C _{> 20} fatty acid esters which contain, inter alia, polyunsaturated fatty acid esters. Although esters of monofunctional alcohols are preferred, the use of esters of polyfunctional alcohols, such as triglycerides, is also possible.

Preference is given to the use of fatty acids and their esters from natural sources, for example from vegetable oils. Particularly preferred for obtaining esters of erucic acid are the seeds of erucic acid-containing rapeseed and sea kale varieties, for example of Abyssinian cabbage.

The molar ratio of the fatty acid ester, preferably erucic acid ester, to the molar amount of palladium in the catalyst used according to the invention is generally from 10,000,000: 1 to 10: 1, preferably from 1,000,000: 1 to 100: 1, more preferably from 10,000: 1 to 500 : 1.

Carbonylation of C _{> 20} fatty acid esters leads to esters of odd linear C _{> 21} α, ω-dicarboxylic acids when esters of even-numbered fatty acids are used.

The α, ω-dicarboxylic acids and their esters according to the invention are suitable as monomers for the preparation of polycondensates according to the invention.

Also suitable are reactive derivatives of these acids, such as acid halides, activated esters, anhydrides or imidazolides.

Likewise suitable, for example in combination with the diacids or diesters, are the corresponding α, ω-diols which are obtained from the diacids / diesters according to known reduction methods familiar to the person skilled in the art.

Using known methods for the reduction of carboxylic acid derivatives to alcohols, for example, 1,23-diethyl tricosanedioate could be converted to> 99% pure 1,23-dihydroxy tricosane. Examples of suitable methods for the reduction of carboxylic acids or their derivatives to alcohols are the catalytic hydrogenation with hydrogen, the reduction by inorganic hydridic reagents, and the reduction by organic compounds with oxidation of the same.

Furthermore, the α, ω-dicarboxylic acids prepared according to the invention and their esters, as well as the α, ω-diols obtainable therefrom, can be converted into the corresponding α, ω-diamines by known methods known to the person skilled in the art, which in turn are used as monomers in the synthesis Can be used according to the invention polycondensates. Examples of known methods for reacting carboxylic acids or their esters to amino groups are amidation, followed by dehydration, and hydrogenation; for converting alcohols to amines, halogenation or tosylation, followed by reaction with ammonia or alternatively conversion to the azide followed by reduction. To produce diisocyanates, the amines can be reacted with phosgene or phosgene equivalents.

Esters of linear odd number C _≥23 aliphatic α, ω-dicarboxylic acids, and linear odd number C _≥23 aliphatic α, ω-diols can be converted to polymers which are an object of the invention. The diesters can be used as such or in activated form, for example as acids, as chlorides, or Anhydrides, can be used ..; 1,23-Tricosanedicarboxylic acid or its esters, 1,23-tricosanediol, 1,23-tricosanediamine and 1,23-tricosanediisocyanate are preferably used for the reaction to give polymers. Particular preference is given to using 1,23-tricosanedicarboxylic acid or its esters.

In addition to at least one of the α, ω-difunctional compounds according to the invention, which can be obtained according to the invention, other polyfunctional alcohols, amines, acids or their esters, chlorides or anhydrides, cyclic lactams or lactones and isocyanates can also be used in the preparation of the polymers according to the invention. In addition to the functional groups mentioned, these may also contain further heteroatoms. Examples of suitable alcohols are ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, cyclohexanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 1, 18-octadecanediol , 1,19-nonadecanediol, 2,2-di (4-hydroxyphenyl) propane, diethylene glycol, dihydroxy-terminated polyethylene glycol and trimethylolpropane, and aromatic di- and polyhydroxy compounds such as 4,4'-dihydroxybiphenyl and bisphenols such as bisphenol A and bisphenol AF. Examples of suitable amines are ethylenediamine, diethylenetriamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,10-diaminodecane, 1,12-diaminododecane and aromatic diamines such as p-phenylenediamine. Examples of suitable carboxylic acids are maleic acid, succinic acid, fumaric acid, adipic acid, sebacic acid, 1,19-nonadecanedioic acid, phthalic acid, terephthalic acid. Examples of suitable lactams are ε-caprolactam, laurolactam. Examples of suitable lactones are ε-caprolactone and butyrolactone. Examples of suitable diisocyanates are hexamethylene diisocyanate and 4,4'-diphenylmethane diisocyanate.

Preference is given to 1,23-tricosanedicarboxylic acid or its esters of monofunctional alcohols, in the presence or absence of further exemplified in the preceding paragraph dicarboxylic acids or their esters, reacted with one or more diols, diamines, optionally in the presence of lactams. Suitable diols, diamines and lactams are exemplified in the preceding paragraph.

More preferably, 1,23-tricosanedicarboxylic acid is polycondensed with one or more of the following compounds: ethylene glycol, 1,3-propanediol, 1,4-butanediol, cyclohexanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol , 1,18-octadecanediol, 1,19-nonadecanediol, 1,23-tricosanediol 2,2-di (4-hydroxyphenyl) propane, diethylene glycol, dihydroxy-terminated polyethylene glycol, ethylenediamine, diethylenetriamine, 1,3-diaminopropane, 1.4 Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,10-diaminodecane, 1,12-diaminododecane, 1,23-tricosanediamine.

Likewise particularly preferably, the α, ω-dicarboxylic acid used according to the invention, preferably 1,23-tricosanedicarboxylic acid, together with succinic acid, adipic acid and / or terephthalic acid, is polycondensed with one or more of the following compounds: ethylene glycol, 1,3-propanediol, 1,4- Butanediol, cyclohexanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, 1,23-tricosanediol, 2,2-di (4-hydroxyphenyl) propane, diethylene glycol, dihydroxy-terminated polyethylene glycol, ethylenediamine, diethylenetriamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,10-diaminodecane, 1,12-diaminododecane, 1 23-Tricosandiamin.

Polymerization processes are well known to the person skilled in the art. The polymerization can be carried out in the presence or absence of catalysts, solvents, suspending agents or other additives. The polymerization can be carried out, for example, in solution, melt, suspension, nonaqueous or aqueous dispersion. Suitable catalysts are, for example, organic or inorganic acids; as well as alkoxides, carboxylates and oxides of transition or main group metals. The polymerization takes place at 0.00001 mbar to 100 bar pressure. To remove volatile by-products, the polymerization can be carried out in vacuo. The polymerization mixture can be forcibly mixed, for example by stirrer or extruder. The polymerization can be carried out in one or more stages.

Optionally, crosslinking can take place during or after the polymerization by means of suitable reagents. As a result, certain properties, such as elasticity or flow properties, can be obtained or improved.

Furthermore, the properties of the polycondensates according to the invention can be modified by chain extension, for example by reaction with carbonylbiscaprolactam (CBC) and / or phenylene-1,4-bis-oxazoline (1.4-PBO). Further suitable methods of chain extension are, for example, the reaction with polyfunctional isocyanates. The polymers according to the invention can be used as prepolymers in polycondensations and polyadditions. For example, dihydroxy-terminated polymers according to the invention can be reacted with polyfunctional isocyanates or carboxylic acids.

In a preferred embodiment, the group Z, Z 'in the formula (I) correspond to -XC (= O) - or -X'-C (= O) - where X, X' are identical or different, preferably identical, O or NH , preferably O, are.

This embodiment relates to polycondensates containing repeating units -XC (= O) - (CH ₂ ) _{2n + 1} -C (= O) -X '- with n≥10 and X, X' O or NH.

Also preferred are polycondensates in which Z is a group -C (= O) -O-CH ₂ ~, -C (= O) -NH-CH ₂ ~, -NH-C (= O) -O-CH ₂ ~ or -OC (= O) -NH-CH ₂ ~, ie polycondensates containing repeating units -M- (CH ₂ ) _{2n + 3} -M'-, where n≥10 and M, M 'an amide, ester - or urethane function mean.

Also preferred are copolyesters which contain, in addition to a monomer according to the invention, further monomers, preferably polyester [{-A ¹ -OC (OO) - (CH ₂ ) _{2n + 1} -C (OO) O-} _x {-A ¹ - OC (= O) -A ² -C (= O) O-} _y ], where n ≥10 and A ¹ , A ^{2 is} a C ₂ to C _{36 is} aliphatic, cycloaliphatic, aromatic or mixed radical. For example, a mixed residue is an araliphatic group. x and y respectively denote the mole fraction, ie x + y = 1.

Also preferred are copolyamides which, in addition to a monomer according to the invention, comprise further monomers, in particular polyamides [{-A ³ -NHC (OO) - (CH ₂ ) _{2n + 1} -C (OO) NH} _x {-A ³ -NHC (= O) -A ⁴ -C (= O) NH-} _y ], where n ≥10 and A ³ , A ⁴ each represent an aliphatic, cycloaliphatic, aromatic or mixed radical having 2 to 36 carbon atoms ,

Also preferred are polyesters and polyamides according to the invention with y = 0.

Preference is furthermore given to polycondensates according to the invention where n = 10, in which at least some of the monomers derive from 1,23-tricosanedicarboxylic acid.

The polymers according to the invention generally contain at least 1 mol%, preferably at least 10 mol%, particularly preferably 50 mol% of at least one type of repeating units of the formula (I), preferably of the repeat units - XC (= O) - (CH ₂ ) _{2n + 1} -C (= O) -X'- or -M- (CH ₂ ) _{2n + 3} -M '-; with n ≥ 10, where X, X 'independently of one another are identical or different O or NH; M, M ', independently of one another or different, denote an amide, ester or urethane function.

The polycondensates according to the invention, in particular polyesters, generally have a number-average molecular weight M _{n of} from 1,000 to 2,000,000 s / mol, preferably from 5,000 to 200,000 g / mol and more preferably from 10,000 to 50,000 g / mol.

One advantage of the polycondensates according to the invention, in particular polyesters, is, on the one hand, that they can be prepared on the basis of renewable materials, for example erucic acid esters, based on, for example, sea kale. Another advantage of the polycondensates according to the invention, especially polyester, is that they are basically suitable as biodegradable polymers. In the context of the invention, biodegradable polymers are understood as meaning those materials which are degraded by microorganisms, enzymes or hydrolysis, for example in the soil. The biodegradability test is carried out by the DIN standard EN 13432. The biodegradable materials must be degraded within 6 to 10 weeks in a large composting. In a further embodiment, the invention thus relates to a polyester according to the invention which is biodegradable. The long chain crystalline segments desirably affect melt and crystallization properties and are sufficiently high for thermoplastic processing. Due to their crystallinity, polyesters according to the invention exhibit correspondingly high melting and crystallinity points, which may be, for example, at T _m > 80 ° C. and T _c > 70 ° C., in particular T _m > 90 ° C. and T _c > 75 ° C. Furthermore, the systems show low water absorption.

The polymers according to the invention can be advantageously used in numerous applications, for example in moldings, coatings, foams, films, films and fibers. The polymers according to the invention can also be used in mixtures with other plastics.

Examples of processes for processing the polymer of the invention include injection molding, coextrusion, film casting, blow molding, film blowing, calendering, melt pressing, wet spinning, dry spinning, melt spinning, deep drawing, powder coating and coating from organic solution or aqueous dispersions.

The invention is explained in more detail by the examples without thereby limiting them.

Examples A Preparation of the monomers Example 1 Preparation of 1.23 Diethyl tricosanedioate

A mixture of 10 mL of ethanol, 1.79 g of ethyl erucate, 0.079 mmol of palladium (II) acetate, 0.39 mmol of 1,2- bis [(di-tert-butylphosphino) methyl] benzene and 0.79 mmol of methanesulfonic acid was added in a pressure reactor for 22 h 90 ° C and 20 bar carbon monoxide pressure. The reaction mixture was concentrated on a rotary evaporator at 200 mbar and 50 ° C. Subsequently, 5 mL dichloromethane were added. The mixture was filtered and concentrated on a rotary evaporator at normal pressure and 50 ° C. The residue was recrystallized from ethanol. Yield 76% based on ethyl erucate used. According to ¹ H NMR spectrum,> 99% is 1,23-diethyl tricosanedioate.

(Comparative Example)

A mixture of 10 mL of methanol, 1.79 g of methyl erucate (95%), 0.079 mmol of palladium (II) acetate, 0.39 mmol of 1,2- bis [(di-tert-butylphosphino) methyl] benzene and 0.79 mmol of methanesulfonic acid was in a pressure reactor stirred for 22 h at 90 ° C and 20 bar carbon monoxide. The mixture predominantly contains the non-carbonylated monocarboxylic acid methyl ester.

example 2 Preparation of 1,23-tricosanedicarboxylic acid

A total of 55.2 mmol KOH were added to a suspension of 20 ml of methanol and 4.5 mmol of 1,23-diethyl tricosanedioate. The mixture was heated to reflux with stirring for 10 hours. Subsequently, the solvent was removed in vacuo. To the resulting white solid was added 30 mL of water and acidified to pH = 2 with 6 N hydrochloric acid. The mixture was filtered and the white solid recrystallized from methanol. Yield 96% based on 1,23-diethyl tricosandioate used. According to ¹ H NMR spectrum,> 99% is 1,23-tricosanedicarboxylic acid.

Example 3 Preparation of 1,23-tricosanediol (Route A)

2.3 mmol of 1,23-diethyl tricosanedioate were dissolved in 10 ml of tetrahydrofuran. This solution was slowly added dropwise with stirring to a suspension of 5.2 mmol lithium aluminum hydride in 10 mL tetrahydrofuran. The mixture was heated to reflux with stirring for one hour and then stirred at room temperature overnight. While stirring, 0.2 mL of water, 0.2 mL of 15% aqueous NaOH solution, and 0.6 mL of water were added successively. The mixture was filtered at 40 ° C. The filtrate was concentrated on a rotary evaporator at 50 ° C and 500 mbar. The residue was recrystallized from ethanol. Yield 80% based on 1,23-Diethyltricosandioat used. According to ¹ H NMR spectrum,> 99% is 1,23-dihydroxytricosan.

Example 4 Preparation of 1,23-tricosanediol (Route B)

A mixture of 40 mL tetrahydrofuran, 5.6 mmol 1,23-Diethyltricosandioat, 5.6 .mu.mol Dichlorobis [2- (diphenylphosphino) ethylamine] ruthenium and 0.56 mmol sodium methanolate were stirred in a pressure reactor for 22 hours at 100 ° C and 50 bar hydrogen pressure. The reaction mixture was filtered at 40 ° C. The filtrate was concentrated on a rotary evaporator at 50 ° C and 500 mbar. The residue was recrystallized from toluene. Yield 78% based on 1,23-Diethyltricosandioat used.

B polycondensations and polycondensates example 5 polyesters (23,23)

1.4 mmol of 1,23-diethyl tricosanedioate, 1.4 mmol of 1,23-dihydroxy tricosane and 0.28 mmol titanium tetrabutoxide were heated from 110 ° C. to 150 ° C. in the course of 17 h in a 10 mL flask with a tap at 0.01 mbar. After cooling, a white solid was obtained.

Gel permeation chromatography (solvent 1,2,4-trichlorobenzene, 160 ° C, against linear polyethylene standards) gave a molecular weight of M _n 10 ⁴ g mol ^-1 (M _w / M _n 2). Differential heat flow calorimetry (DSC) shows a peak melting point of T _m 99 ° in the first and second heating curve, a crystallization temperature of 84 ° C, and a melting enthalpy of 180 J g ^-1 .

example 6 polyesters (23,12)

2.8 mmol of 1,23-diethyl tricosanedioate and 1,12-dodecanediol with 0.028 mmol titanium tetrabutoxide in 0.1 ml toluene were heated from 100 ° C. to 220 ° C. over a period of 8 hours in a 100 ml Schlenk with mechanical stirrer. Then it was stirred at 220 ° C and 0.01 mbar for 1 hour. After cooling, a white solid was obtained.

Differential heat flux calorimetry (DSC) shows a peak melting point of T _m 101 ° C in the second heating curve, a crystallization temperature of T _c 76 ° C and a melting enthalpy of ΔH _m 156 J g ^-1 .

Example 7 Polyester (23,6)

2.8 mmol of 1,23-diethyl tricosanedioate and 1,6-hexanediol with 0.028 mmol titanium tetrabutoxide in 0.1 ml toluene were heated from 100 ° C. to 220 ° C. over a period of 8 hours in a 100 ml Schlenk with mechanical stirrer. Then it was stirred at 220 ° C and 0.01 mbar for 1 hour. After cooling, a white solid was obtained.

Differential heat flux calorimetry (DSC) shows a peak melting point of T _m 92 ° C in the second heating curve, a crystallization temperature of T _c 75 ° C and a melting enthalpy of ΔH _m 145 J / g.

Example 8 Polyester (23.4)

2.8 mmol of 1,23-diethyl tricosanedioate and 1,4-butanediol with 0.028 mmol titanium tetrabutoxide in 0.1 ml toluene were heated from 100 ° C. to 200 ° C. over a period of 4 hours in a 100 ml Schlenk with mechanical stirrer. It was then stirred at 220 ° C and 8 hours and another hour at 220 ° C and 0.01 mbar. After cooling, a white solid was obtained. Differential heat flux calorimetry (DSC) shows a peak melting point of T _m 85 ° C in the second heating curve, a crystallization temperature of T _c 71 ° C and a melting enthalpy of ΔH _m 172 J g ^-1 .

Example 9 Polyamide (23,23)

From 1.04 mmol of 1,23-diaminotricosan and 1.04 mmol of 1,23-tricosanedicarboxylic acid, tricosamethylenediamine tricosanedioate was prepared in 9 ml of ethanol.

In a 100 ml Schlenk with mechanical stirrer 1.04 mmol Tricosamethylenediamintricosandioat with 0.037 mmol of 1,23-diaminotricosan over a period of 3 hours from 120 ° C to 210 ° C under an argon atmosphere and stirred for 1.5 hours at this temperature. Subsequently, a vacuum of 1 × 10 ^-5 bar was applied at 210 ° C. for 17.5 hours. After cooling, a beige solid was obtained.

Differential heat flux calorimetry (DSC) shows a peak melting point of T _m 151 ° C in the second heating curve, a crystallization temperature of T _c 130 ° C, and a melting enthalpy of ΔH _m 88 J g ^-1 .

Example 10 Polyamide (12,23)

From 1.43 mmol of 1,12-diaminododecane and 1.43 mmol of 1,23-tricosanedicarboxylic acid, dodecamethylenediamine tricosanedioate was prepared in 9 ml of ethanol.

In a 100 mL Schlenk with mechanical stirrer 1.43 mmol Dodecamethylenediamintricosandioat with 0.045 mmol of 1,12-diaminododecane over a period of 5.5 hours from 100 ° C to 200 ° C under an argon atmosphere and stirred for 16.5 hours at this temperature. Subsequently, a vacuum of 1 × 10 ^-5 bar was applied at 200 ° C for 4 hours. After cooling, a beige solid was obtained.

Differential heat flow calorimetry (DSC) shows a peak melting point of T _m 168 ° C in the second heating curve, a crystallization temperature of T _c 150 ° C and a melting enthalpy of ΔH _m 121 J g ^-1 .

Example 11 Polyamide (23,19)

From 1.06 mmol of 1,23-diaminotricosan and 1.06 mmol of 1,19-nonadecanedicarboxylic acid, tricosamethylenediamine monadecanedioate was prepared in 8 ml of ethanol.

In a 100 mL Schlenk with mechanical stirrer 1.06 mmol Tricosamethylenediaminnonadecandioat over a period of 4.5 hours of Heated to 100 ° C at 230 ° C under an argon atmosphere and stirred for 1.25 hours at this temperature. Subsequently, a vacuum of 1 × 10 ^-5 bar was applied at 230 ° C. for 16.5 hours. After cooling, a beige solid was obtained.

Differential heat flux calorimetry (DSC) shows a peak melting point of T _m 156 ° C in the second heating curve, a crystallization temperature of T _c 132 ° C and a melting enthalpy of ΔH _m 85 J g ^-1 .

Claims (15)

1. A polycondensate comprising one or more repeat units of the formula (I),
   
           -Z-(CH₂)_2n+1-Z'-     (I)
   
   in which the symbols and indices have the following meanings:

   Z, Z' is identical or different and is -X-C(=O)∼, -C(=O)-HN-CH₂∼, -C(=O)-O-CH₂∼, -NH-C(=O)-O-CH₂∼, -O-C(=O)-NH-CH₂∼;

   X is O or NH;

   ∼ indicates the bond to the group (CH₂)_n and

   n is a number ≥ 10.
2. The polycondensate according to claim 1, comprising repeat units -X-C(=O)-(CH₂)_2n+1-C(=O)-X'-where n ≥ 10 and X, X' = O or NH.
3. The polycondensate according to claim 1, comprising repeat units -M-(CH₂)₂₊₃-M'∼ where n is ≥ 10 and M, M' is an amide function (-C(=O)-NH∼), ester function (-C(=O)-O∼) or urethane function (-NH-C(=O)-O∼).
4. The polyester according to claim 1 or 2 with repeat units [{-A¹-OC(=O)-(CH₂)_2n+1-C(=O)O-}_x{-A¹-OC(=O)-A²-C(=O)O-}_y] where n ≥ 10 and A¹, A² are identical or different and are a C₂ to C₃₆ aliphatic, cycloaliphatic, aromatic or mixed radical and x + y = 1.
5. The polyamide according to claim 1 or 2 with repeat units [{-A1-NHC(=O)-(CH2)2n+1-C(=O)NH-}x{-A1-NHC(=O)-A2-C(=O)NH-}y] where n ≥ 10 are C₂ to C₃₆ aliphatic, cycloaliphatic, aromatic or mixed radical and x + y = 1.
6. The polycondensate according to claim 3 or 4, where y = 0.
7. The polycondensate according to any one of claims 1 to 6 where n = 10.
8. The polycondensate according to any one of claims 1 to 7, comprising at least 1 mol% of one or more repeat units of the formula (I).
9. A method for producing a polycondensate according to any one of claims 1 to 8, where at least one monomeric compound of the formula (II)
   
           Z¹-(CH₂)_2n+1-Z^1'     (II)
   
   in which

   Z¹, Z¹' is ∼C(=O)-Q or ∼CH₂-NCO;

   Q is identical or different and is OH, halogen or C₁-C₁₀-alkoxy;

   ∼ indicates the bond to the group (CH₂)_2n+1 and

   n is a number ≥ 10,

   is polycondensed with at least one di- or polyol or at least one di- or polyamine,
   and/or
   at least one monomeric compound of the formula (III),
   
           Z²-(CH₂)_2n+1-Z^2'     (III)
   
   in which

   Z, Z' is identical or different and is HO-CH₂∼ or H₂N-CH₂∼;

   ∼ indicates the bond to the group (CH₂)_n and

   N is a number ≥ 10,

   is polycondensed with at least one di- or polycarboxylic acid, a reactive derivative of such a di- or polycarboxylic acid or at least one di-or polyisocyanate.
10. The use of a polycondensate according to any one of claims 1 to 8 in moldings, coatings, foams, films, foils and/or fibers.
11. A molding, coating, foil, foam or fiber comprising one or more polycondensates according to any one of claims 1 to 8.
12. A method for producing saturated or unsaturated α,ω-dicarboxylic acids or esters having in each case 2n + 3 carbon atoms in the acid moiety, where n is ≥ 10, comprising the step of a hydroxy- or alkoxycarbonylation of a mono- or polyunsaturated fatty acid ester having 2n + 2 carbon atoms in the acid moiety, where n is ≥ 10, in the presence of a catalyst comprising at least one palladium compound and at least one phosphane, at a temperature in the range from 85 to 100°C and a pressure from 3 to 80 atm.
13. The method according to claim 12, where the alkoxy compound is a C₂-C₃₆-alcohol.
14. The method according to claim 12 or 13, where the catalyst comprises a palladium(II) salt and 1,2-bis[(di-tert-butylphosphino)methyl]benzene.
15. The method according to any one of claims 12 to 14, where the fatty acid ester is an ester of erucic acid.